EP2468822B1 - Black trisazo dyes, their preparation and their use - Google Patents

Black trisazo dyes, their preparation and their use Download PDF

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Publication number
EP2468822B1
EP2468822B1 EP10196679.4A EP10196679A EP2468822B1 EP 2468822 B1 EP2468822 B1 EP 2468822B1 EP 10196679 A EP10196679 A EP 10196679A EP 2468822 B1 EP2468822 B1 EP 2468822B1
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EP
European Patent Office
Prior art keywords
group
radical
general formula
coom
trisazo
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EP10196679.4A
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German (de)
French (fr)
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EP2468822A1 (en
Inventor
Kurt Baettig
Damien Moigno
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Rex-Tone Industries Ltd
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Rex-Tone Industries Ltd
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Priority to EP10196679.4A priority Critical patent/EP2468822B1/en
Priority to AU2011253851A priority patent/AU2011253851B2/en
Priority to JP2011280567A priority patent/JP5712406B2/en
Priority to CN201110432311.1A priority patent/CN102558899B/en
Priority to KR1020110138862A priority patent/KR20120089999A/en
Priority to US13/335,219 priority patent/US8361168B2/en
Publication of EP2468822A1 publication Critical patent/EP2468822A1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B33/00—Disazo and polyazo dyes of the types A->K<-B, A->B->K<-C, or the like, prepared by diazotising and coupling
    • C09B33/18—Trisazo or higher polyazo dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B33/00—Disazo and polyazo dyes of the types A->K<-B, A->B->K<-C, or the like, prepared by diazotising and coupling
    • C09B33/18—Trisazo or higher polyazo dyes
    • C09B33/22—Trisazo dyes of the type A->B->K<-C
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/16—Writing inks
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/02—Material containing basic nitrogen
    • D06P3/04—Material containing basic nitrogen containing amide groups
    • D06P3/32—Material containing basic nitrogen containing amide groups leather skins
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/28—Colorants ; Pigments or opacifying agents
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/30—Luminescent or fluorescent substances, e.g. for optical bleaching

Definitions

  • the invention relates to novel black trisazo dyes and their salts, to a process for their preparation, to their use in dyeing and printing processes and to dye preparations containing these trisazo dyes, in particular water-based inks for ink-jet printing and writing utensils.
  • customized recording materials for such printers include nanoporous inorganic compounds, such as silica, alumina / hydroxide, alumina, or mixtures thereof, having a modified surface.
  • nanoporous recording materials are known by the term "nanoporous recording materials”. Images printed on these recording materials must have good durability even under unfavorable conditions, which is only possible with a finely tuned system of inks (or the dyes contained therein).
  • the trisazo dye of the formula (I) is in the patent application WO 2005/054 374 (Example No. 5).
  • the trisazo dye of the formula (II) is in the patent application US 6,632,932 B1 (Example No. 14).
  • the trisazo dye of the formula (III) is in the patent application JP 2005/220211 (Example No. 1).
  • Dyes for such inks must have a good solubility in the majority of aqueous ink liquid, they must penetrate into the recording material and must not show aggregation on the surface of the recording material ("bronzing"). They must give images with a high optical density, a good water resistance, a good light resistance, a good ozone resistance and a good diffusion resistance even under unfavorable conditions. They must be stable in the ink, even if stored for a long time under unfavorable conditions.
  • Typical inks contain one or more dyes or pigments, water, organic co-solvents, and other additives.
  • the aim of the invention is the provision of new black trisazo dyes with black, neutral as possible shade and their use in aqueous inks, especially in ink jet printing and in writing utensils.
  • ink-jet printing they are particularly advantageous for producing images or dyeings on fast-drying, nanoporous recording materials.
  • These new high-color black trisazo dyes have a high solubility in aqueous formulations, giving images or dyeings with generally good properties, especially in ink-jet printing, where they give brilliant color images that are not or at most insignificant even after prolonged storage at high temperature and humidity Extent be blurred and also lightfast and ozone resistant.
  • Another object of the invention is to provide liquid dye preparations, in particular ink jet printing inks and writing utensils, which give a spectrally unaltered hue on all possible recording materials.
  • Another object of the invention is to provide inks that meet all the aforementioned requirements.
  • trisazo dyes of the general formulas (IV) and (V) in which R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , M, o and p have the same meaning as previously stated and the sulfonic acid groups are in positions 4 and 4 '.
  • trisazo dyes of the general formulas (IV) and (V) in which A is a radical of the general formula (VI) and B is a radical of the general formula (VIII).
  • Preferred metal cations are the cations of the alkali metals (Li, Na, K, Rb, Cs), the alkaline earth metals (Mg, Ca, Sr, Ba) and the ammonium cation which optionally has one or more alkyl radicals each having 1 to 4 carbon atoms or with one Hydroxyl group substituted alkyl having in each case 1 to 6 carbon atoms.
  • trisazo dyes of the general formula (IV) are as follows, wherein the substituent M is specified in Table 1.
  • trisazo dyes of the general formula (IV) are as follows, wherein the substituent M is specified in Table 1.
  • the trisazo dyes of the general formulas (IV) and (V) can be present as free acids or as inorganic or organic salts of these acids. Preferably, they are in the form of their alkali or ammonium salts, wherein the ammonium cation may be substituted.
  • Examples of such substituted ammonium cations are 2-hydroxyethylammonium, bis (2-hydroxyethyl) ammonium, tris (2-hydroxyethyl) ammonium, bis (2-hydroxyethyl) methyl ammonium, tris [2- (2-methoxyethoxy ) -ethyl] -ammonium, 8-hydroxy-3,6-dioxaoctylammonium and tetraalkylammonium such as tetramethylammonium or tetrabutylammonium.
  • the invention relates not only to pure trisazo dyes of the general formulas (IV) and (V), but also to mixtures of these trisazo dyes.
  • the invention furthermore relates to a process for the preparation of the trisazo dyes of the formula (IV) according to the invention, which is characterized in that an amine of the general formula (X) in which n and M have the same meaning as stated above, diazotized and then with a compound of general formula (XI), where m and M have the same meaning as before, is coupled at an acidic pH between about 1.0 and 3.0, that the intermediate dye of the general formula (XII) is formed.
  • the intermediate dye of the general formula (XII) is further treated with a diazo compound of the general formula (XIII) in which R 1 , R 2 , R 3 , R 4 and R 5 have the same meaning as stated above and X is the anion of the acid used in the diazotization, or the general formula (XIV) wherein R 15 , R 16 , R 17 , R 18 and p have the same meaning as before and X is the anion of the acid used in the diazotization, coupled at a slightly basic pH between about 7.0 and 9.0 and then hydrolyzed basic, such that the intermediate dyes of the general formula (XV) or the general formula (XVI) be formed.
  • a diazo compound of the general formula (XIII) in which R 1 , R 2 , R 3 , R 4 and R 5 have the same meaning as stated above and X is the anion of the acid used in the diazotization
  • XIV wherein R 15 , R 16 , R 17 , R 18 and p have
  • the invention further relates to a process for preparing the novel trisazo dyes of the general formula (V), which is characterized in that an amine of the general formula (XIX) wherein M, A and n have the same meaning as stated above, diazotized and then with a compound of general formula (XX) wherein M, B and m have the same meaning as before, is coupled at a slightly basic pH between about 7.0 and 9.0, so that the novel trisazo dyes of the general formula (V) are formed.
  • the trisazo dyes of the general formulas (IV) and (V) according to the invention dye cellulosic materials, paper, cotton and viscose, as well as leather and wool with good wet and light fastness properties.
  • the trisazo dyes can be used in accordance with all common practice in the paper and textile industry for substantive dyes, in particular in the bulk and surface treatment of paper for sized or unsized Sorts. They can also be used in the yarn and piece dyeing of cotton, viscose and linen by the exhaust process or in a continuous process.
  • novel trisazo dyes are particularly suitable for recording writing and images on a recording material, coated or uncoated paper, for dyeing and printing natural or synthetic fiber materials, nanoporous recording materials, leather and aluminum.
  • the invention further relates to liquid dye preparations containing at least one trisazo dye of the general formulas (IV) or (V).
  • This application form is particularly preferred in the dyeing of paper.
  • Trisazo dyes or mixtures of trisazo dyes of the general formulas (IV) and (V) are excellent dyes for the production of inks for ink-jet printing and writing utensils.
  • inventive black trisazo dyes of the general formulas (IV) and (V) are good with other Nuancierfarbstoffen, in particular those, such as those in the patent applications EP 0'755'984 .
  • WO 96/24635 and WO 96/24636 can be combined to obtain a more neutral black color.
  • Such an ink contains one or more of the trisazo dyes according to the invention in a liquid aqueous solvent.
  • the ink contains 0.5 to 20 percent by weight, preferably 0.5 to 8 percent by weight of these trisazo dyes, based on the total weight of the ink.
  • the liquid solvent is preferably water or a mixture of water and water-miscible organic solvents. Suitable solvents are, for example, in the patent US 4,626,284 and the patent applications GB 2'289'473 .
  • EP 0'176'195 EP 0'415'581 .
  • EP 0'425'150 and EP 0'597'672 been described. The present invention will be further described by the following examples, without thereby limiting the claimed compounds in any way.
  • Trisazo Dye No. 10 was prepared as follows:
  • the diazo suspension B was added to the suspension of the intermediate dye of the formula (XXIX) with stirring for 30 minutes and the pH was maintained at between 5.0 and 7.0 by metering in sodium hydroxide (20%). After completion of the addition, the mixture was further stirred for 2 hours at a temperature between 0 ° C and 5 ° C and 2 hours at room temperature.
  • the intermediate dye of formula (XXVI) was not isolated and hydrolyzed directly with caustic soda at a temperature of 90 ° C and a pH between 11.0 and 12.0. After completion of the hydrolysis, the pH was lowered to 7.0 with acetic acid and the precipitated dye was filtered off with suction. The crude dye was cleaned with 300 ml of an aqueous solution (60%) of ethanol. After the dye had dried, 39.2 g of the dye of the formula (XXIII) were obtained.
  • the trisazo dyes 11 to 26 according to the invention can be prepared.
  • the trisazo dyes (31) to (34) can be prepared by the method described in the patent application EP 10187827.0 has been described.
  • the present invention as far as it relates to inks, is described by the following examples in which trisazo dyes according to the invention from Table 1 and trisazo dyes of the prior art are used.
  • 100 g of each ink was prepared by adding the required amount of dye (2-9 g), glycerol (5 g), ethylene glycol (5 g), Tergitol 15-S-7 (available from Union Carbide Co., Houston, USA) ( 0.5 g) and a biocide solution (Mergal K 10N, available from Riedel-de-Ha ⁇ n, Seelze, Germany) (0.2 g) were heated together with water for about 1 hour with stirring to a temperature of 50 ° C.
  • the resulting solution was cooled to a temperature of 20 ° C and adjusted its pH to 7.5. Subsequently, the solution was filtered through a Millipore ® filter with 0.5 micron pore diameter. The amount of dye was chosen so that the optical density of the printed image for all dyes was as equal as possible.
  • the printed samples are irradiated in a Weather-Ometer® Ci35A (available from Atlas Material Testing Technology, Chicago, USA) with a 6500 W xenon lamp at a temperature of 20 ° C and a relative humidity of 50% until 20 megalux hours were achieved.
  • the density loss was measured with a spectrophotometer Spectrolino ®.
  • the percent density loss from the original density is a measure of the light fastness of the dyes on the printed recording material.
  • the L * a * b * values were measured on printed samples using a spectrometer Gretag SPM 100, available from Gretag AG, Regensdorf, Switzerland.
  • L * a * b * values (type of light D 65 ) are listed in Table 3 for the novel and for the trisazo black dyes (I) and (II) of the prior art.
  • Table 3 Dye no. L * a * b * value Recording material 1 L * a * b * value recording material 2 10 15.4 / 4.5 / -1.9 11.9 / 4.9 / -2.3 11 7.8 / 5.7 / -7.4 7.2 / 4.5 / -8.0 12 10.8 / 6.4 / -9.6 9.8 / 11.9 / -3.0 13 7.8 / 5.7 / -7.4 7.2 / 4.5 / -8.0 14 6.3 / 1.6 / -5.8 6.3 / 1.7 / -6.2 15 8.9 / 2.4 / -5.6 7.8 / 2.8 / -6.9 16 8.1 / 3.4 / -5.8 8.6 / 3.4 / -7.1 17 17.0 / 10.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
  • Coloring (AREA)
  • Ink Jet (AREA)

Description

Technisches GebietTechnical area

Die Erfindung bezieht sich auf neue schwarze Trisazofarbstoffe und ihre Salze, ein Verfahren zu ihrer Herstellung, ihren Einsatz in Färbe- und Druckverfahren sowie auf Farbstoffpräparationen, die diese Trisazofarbstoffe enthalten, insbesondere wässrige Tinten für den Tintenstrahldruck und Schreibutensilien.The invention relates to novel black trisazo dyes and their salts, to a process for their preparation, to their use in dyeing and printing processes and to dye preparations containing these trisazo dyes, in particular water-based inks for ink-jet printing and writing utensils.

Stand der TechnikState of the art

Tintenstrahldrucker der neusten Generation müssen aus wirtschaftlichen Gründen immer schneller drucken können. Angepasste Aufzeichnungsmaterialen für solche Drucker enthalten nanoporöse anorganische Verbindungen, beispielsweise Siliziumdioxid, Aluminiumoxid/hydroxid, Aluminiumoxid oder deren Gemische, mit einer modifizierten Oberfläche. Solche Aufzeichnungsmaterialien sind unter dem Begriff "nanoporöse Aufzeichnungsmaterialen" bekannt. Auf diese Aufzeichnungsmaterialien gedruckte Bilder müssen eine gute Haltbarkeit auch unter ungünstigen Bedingungen aufweisen, was nur möglich ist mit einem fein abgestimmten System von Tinten (beziehungsweise den darin enthaltenen Farbstoffen).For the most economical reasons, ink jet printers of the latest generation must be able to print faster and faster. Customized recording materials for such printers include nanoporous inorganic compounds, such as silica, alumina / hydroxide, alumina, or mixtures thereof, having a modified surface. Such recording materials are known by the term "nanoporous recording materials". Images printed on these recording materials must have good durability even under unfavorable conditions, which is only possible with a finely tuned system of inks (or the dyes contained therein).

Bis jetzt können diese Bilder nicht alle an sie gestellten Anforderungen erfüllen, insbesondere lässt häufig die Wasserfestigkeit, die Lichtbeständigkeit, die Ozonbeständigkeit, der Farbton und die Brillanz der auf diesen Materialien hergestellten Bilder zu wünschen übrig. Es werden deshalb Farbstoffe gesucht, welche die obigen Eigenschaften, besonders in schwarzen Farbtönen, der auf diesen Materialien hergestellten Bilder verbessern.Until now, these images can not meet all the requirements imposed on them, in particular, the water resistance, the light resistance, the ozone resistance, the color tone and the brilliance of the images produced on these materials often leave much to be desired. Therefore, dyes are sought which improve the above properties, especially in black shades, of the images formed on these materials.

Obwohl schon eine ganze Anzahl verschiedener schwarzer Farbstoffe zur Verwendung im Tintenstrahldruck vorgeschlagen worden sind, vermag noch keiner alle an ihn gestellten Anforderungen zu erfüllen.Although a number of different black dyes have been proposed for use in ink-jet printing, none of them are yet able to meet all the requirements imposed on them.

Der Trisazofarbstoff der Formel (I)

Figure imgb0001
wird in der Patentanmeldung WO 2005/054 374 (Beispiel Nr. 5) beschrieben.The trisazo dye of the formula (I)
Figure imgb0001
 is in the patent application WO 2005/054 374 (Example No. 5).

Der Trisazofarbstoff der Formel (II)

Figure imgb0002
wird in der Patentanmeldung US 6,632,932 B1 (Beispiel Nr. 14) beschrieben.The trisazo dye of the formula (II)
Figure imgb0002
 is in the patent application US 6,632,932 B1 (Example No. 14).

Der Trisazofarbstoff der Formel (III)

Figure imgb0003
wird in der Patentanmeldung JP 2005/220211 (Beispiel Nr. 1) beschrieben.The trisazo dye of the formula (III)
Figure imgb0003
 is in the patent application JP 2005/220211 (Example No. 1).

Diese Trisazofarbstoffe des Standes der Technik vermögen in der Praxis im Tintenstrahldruck nicht alle an sie gestellten Anforderungen zu erfüllen, wenn es darum geht, mit ihnen Tinten herzustellen, die auch auf schnelltrocknenden, nanoporösen Aufzeichnungsmaterialien Bilder mit einer guten Haltbarkeit auch unter ungünstigen Bedingungen ergeben. Natürlich müssen sie auch auf allen anderen möglichen Aufzeichnungsmaterialien wie unbeschichtetem oder beschichtetem Papier, beschichtetem oder unbeschichtetem, opaken oder durchsichtigem Kunststoffträger schwarze Bildstellen oder Färbungen mit möglichst neutralem Farbton (L*a*b*-Werte mit möglichst kleinen a*- und b*-Werten) ergeben.
Farbstoffe für solche Tinten müssen eine gute Löslichkeit in der mehrheitlich wässrigen Tintenflüssigkeit aufweisen, sie müssen ins Aufnahmematerial eindringen und dürfen keine Aggregation an der Oberfläche des Aufnahmematerials zeigen ("Bronzing"). Sie müssen Bilder mit einer hohen optischen Dichte, einer guten Wasserfestigkeit, einer guten Lichtbeständigkeit, einer guten Ozonbeständigkeit und einer guten Diffusionsfestheit auch unter ungünstigen Bedingungen ergeben. Sie müssen in der Tinte stabil sein, auch wenn diese lange Zeit unter ungünstigen Bedingungen gelagert wird.These trisazo dyes of the prior art are unable in practice to fulfill all the requirements placed on them in ink jet printing when it comes to making inks which give even on fast drying, nanoporous recording materials images with a good durability even under unfavorable conditions. Of course, on all other possible recording materials, such as uncoated or coated paper, coated or uncoated, opaque or transparent plastic substrates, they must also have black image spots or dyeings with as neutral a color tone as possible (L * a * b * values with as small a * and b * as possible). Values).
Dyes for such inks must have a good solubility in the majority of aqueous ink liquid, they must penetrate into the recording material and must not show aggregation on the surface of the recording material ("bronzing"). They must give images with a high optical density, a good water resistance, a good light resistance, a good ozone resistance and a good diffusion resistance even under unfavorable conditions. They must be stable in the ink, even if stored for a long time under unfavorable conditions.

Verschiedene Zusammensetzungen für Tinten sind vorgeschlagen worden. Typische Tinten enthalten einen oder mehrere Farbstoffe oder Pigmente, Wasser, organische Hilfslösungsmittel und andere Zusätze.Various compositions for inks have been proposed. Typical inks contain one or more dyes or pigments, water, organic co-solvents, and other additives.

Die Tinten müssen die folgenden Anforderungen erfüllen:

  1. (1) Die Tinte ergibt Bilder hochstehender Qualität auf allen möglichen Aufnahmematerialien.
  2. (2) Die Tinte ergibt Bilder mit guter Wasserfestigkeit.
  3. (3) Die Tinte ergibt Bilder mit guter Lichtbeständigkeit.
  4. (4) Die Tinte ergibt Bilder mit guter Ozonbeständigkeit.
  5. (5) Die Tinte ergibt Bilder mit hervorragender Abriebfestigkeit.
  6. (6) Die Tinte ergibt Bilder mit hervorragender Lagerbeständigkeit bei hoher Temperatur und Feuchtigkeit.
  7. (7) Die Tinte verstopft die Tintenstrahldruckerdüsen nicht, auch wenn diese längere Zeit während Druckpausen nicht abgedeckt sind.
  8. (8) Die Tinte kann lange Zeit gelagert werden, ohne dass ihre Qualität abnimmt.
  9. (9) Die Tinte muss ungiftig, unbrennbar und unschädlich sein.
The inks must meet the following requirements:
  1. (1) The ink gives images of superior quality on all kinds of recording materials.
  2. (2) The ink gives images with good water resistance.
  3. (3) The ink gives images with good light resistance.
  4. (4) The ink gives images with good ozone resistance.
  5. (5) The ink gives images with excellent abrasion resistance.
  6. (6) The ink gives images excellent in storage stability at high temperature and humidity.
  7. (7) The ink does not clog the inkjet printer nozzles, even if they are not covered for a long time during printing pauses.
  8. (8) The ink can be stored for a long time without degrading its quality.
  9. (9) The ink must be non-toxic, non-flammable and harmless.

Beschreibung der ErfindungDescription of the invention

Ziel der Erfindung ist die Bereitstellung neuer schwarzer Trisazofarbstoffe mit schwarzem, möglichst neutralem Farbton und deren Verwendung in wässrigen Tinten, insbesondere im Tintenstrahldruck und in Schreibutensilien. Im Tintenstrahldruck sind sie besonders vorteilhaft zur Erzeugung von Bilder oder Färbungen auf schnelltrocknenden, nanoporösen Aufzeichnungsmaterialien. Diese neuen, farbstarken schwarzen Trisazofarbstoffe haben eine hohe Löslichkeit in wässrigen Formulierungen, ergeben Bilder oder Färbungen mit allgemein guten Eigenschaften, insbesondere im Tintenstrahldruck, wo sie Bilder mit brillantem Farbton ergeben, die auch bei längerer Lagerung bei hoher Temperatur und Feuchtigkeit nicht oder höchstens in unbedeutendem Ausmass unscharf werden und ebenso lichtecht und ozonbeständig sind.
Ein weiteres Ziel der Erfindung ist die Bereitstellung von flüssigen Farbstoffpräparationen, insbesondere von Tinten für den Tintenstrahldruck und für Schreibutensilien, die auf allen möglichen Aufnahmematerialien einen spektral unveränderten Farbtone ergeben.
Ein weiteres Ziel der Erfindung ist die Bereitstellung von Tinten, die alle vorhin erwähnten Anforderungen erfüllen.The aim of the invention is the provision of new black trisazo dyes with black, neutral as possible shade and their use in aqueous inks, especially in ink jet printing and in writing utensils. In ink-jet printing, they are particularly advantageous for producing images or dyeings on fast-drying, nanoporous recording materials. These new high-color black trisazo dyes have a high solubility in aqueous formulations, giving images or dyeings with generally good properties, especially in ink-jet printing, where they give brilliant color images that are not or at most insignificant even after prolonged storage at high temperature and humidity Extent be blurred and also lightfast and ozone resistant.
Another object of the invention is to provide liquid dye preparations, in particular ink jet printing inks and writing utensils, which give a spectrally unaltered hue on all possible recording materials.
Another object of the invention is to provide inks that meet all the aforementioned requirements.

Die vorliegende Erfindung bezieht sich auf neue Trisazofarbstoffe der allgemeinen Formel (IV)

Figure imgb0004
und der allgemeinen Formel (V)
Figure imgb0005
 worin

M
für ein Wasserstoffatom, ein Metallkation oder ein Ammoniumkation, welches gegebenenfalls eine oder mehrere unsubstituierte oder substituierte Alkylreste oder Hydroxyalkoxylalkylreste mit jeweils 1 bis 18 Kohlenstoffatomen aufweist, steht;
m, n
unabhängig voneinander den Wert 0 oder 1 annehmen;
A
entweder für einen Rest der allgemeinen Formel (VI)
Figure imgb0006
 worin
R6, R7, R8, R9, R10 unabhängig voneinander für ein Wasserstoffatom, eine SO3M-Gruppe, eine NO2-Gruppe eine COOM-Gruppe, eine CN-Gruppe, ein Halogenatom, einen Esterrest, einen Alkylrest oder Alkoxylrest mit je 1 bis 6 Kohlenstoffatomen, für einen unsubstituierten oder substituierten Amidrest oder Sulfonamidrest mit je bis zu 12 Kohlenstoffatomen, wobei die Substituenten aus der Gruppe bestehend aus COOM, OH, OCH3, NH2, Cl, COOCH3 und COOCH2CH3 ausgewählt werden, stehen;
oder für einen Rest der allgemeinen Formel (VII)
Figure imgb0007
 worin
o den Wert 0 oder 1 annimmt
und
R11, R12, R13, R14 unabhängig voneinander für ein Wasserstoffatom, eine SO3M-Gruppe, eine NO2-Gruppe eine COOM-Gruppe, ein Halogenatom, einen Esterrest, einen Alkoxylrest mit 1 bis 6 Kohlenstoffatomen, für einen unsubstituierten oder substituierten Amidrest oder Sulfonamid-Rest mit je bis zu 12 Kohlenstoffatomen, wobei die Substituenten aus der Gruppe bestehend aus COOM, OH, OCH3, NH2, Cl, COOCH3 und COOCH2CH3 ausgewählt werden, stehen
und
B
entweder für einen Rest der allgemeinen Formel (VIII)
Figure imgb0008
 worin
R1, R2, R3, R4, R5 unabhängig voneinander für ein Wasserstoffatom, eine SO3M-Gruppe, eine NO2-Gruppe eine COOM-Gruppe, eine CN-Gruppe, ein Halogenatom, einen Esterrest, einen Alkylrest oder Alkoxylrest mit je 1 bis 6 Kohlenstoffatomen, für einen unsubstituierten oder substituierten Amidrest oder Sulfonamidrest mit je bis zu 12 Kohlenstoffatomen, wobei die Substituenten aus der Gruppe bestehend aus COOM, OH, OCH3, NH2, Cl, COOCH3 und COOCH2CH3 ausgewählt werden, stehen; oder für einen Rest der allgemeinen Formel (IX)
Figure imgb0009
 worin
p den Wert 0 oder 1 annimmt
und
R15, R16, R17, R18 unabhängig voneinander für ein Wasserstoffatom, eine SO3M-Gruppe, eine NO2-Gruppe eine COOM-Gruppe, ein Halogenatom, einen Esterrest, einen Alkoxylrest mit 1 bis 6 Kohlenstoffatomen, für einen unsubstituierten oder substituierten Amidrest oder Sulfonamid-Rest mit je bis zu 12 Kohlenstoffatomen, wobei die Substituenten aus der Gruppe bestehend aus COOM, OH, OCH3, NH2, Cl, COOCH3 und COOCH2CH3 ausgewählt werden, stehen.
The present invention relates to novel trisazo dyes of the general formula (IV)
Figure imgb0004
 and the general formula (V)
Figure imgb0005
 wherein
M
R ein represents a hydrogen atom, a metal cation or an ammonium cation which optionally has one or more unsubstituted or substituted alkyl radicals or hydroxyalkoxyalkyl radicals each having 1 to 18 carbon atoms;
m, n
independently take the value 0 or 1;
A
either a radical of the general formula (VI)
Figure imgb0006
 wherein
R 6 , R 7 , R 8 , R 9 , R 10 independently represent a hydrogen atom, an SO 3 M group, an NO 2 group, a COOM group, a CN group, a halogen atom, an ester group, an alkyl group or alkoxyl radical each having 1 to 6 carbon atoms, an unsubstituted or substituted amide radical or sulfonamide radical having in each case up to 12 carbon atoms, wherein the substituents from the group consisting of COOM, OH, OCH 3 , NH 2 , Cl, COOCH 3 and COOCH 2 CH 3 are selected;
or for a radical of the general formula (VII)
Figure imgb0007
 wherein
o takes the value 0 or 1
and
R 11 , R 12 , R 13 , R 14 independently represent a hydrogen atom, an SO 3 M group, a NO 2 group, a COOM group, a halogen atom, an ester group, an alkoxyl group having 1 to 6 carbon atoms, for a unsubstituted or substituted amide residue or sulfonamide residue each having up to 12 carbon atoms, said substituents being selected from the group consisting of COOM, OH, OCH 3 , NH 2 , Cl, COOCH 3 and COOCH 2 CH 3
and
B
either a radical of the general formula (VIII)
Figure imgb0008
 wherein
R 1 , R 2 , R 3 , R 4 , R 5 independently represent a hydrogen atom, an SO 3 M group, an NO 2 group, a COOM group, a CN group, a halogen atom, an ester group, an alkyl group or alkoxyl radical each having 1 to 6 carbon atoms, an unsubstituted or substituted amide radical or sulfonamide radical having in each case up to 12 carbon atoms, wherein the substituents from the group consisting of COOM, OH, OCH 3 , NH 2 , Cl, COOCH 3 and COOCH 2 CH 3 are selected; or a radical of the general formula (IX)
Figure imgb0009
 wherein
p takes the value 0 or 1
and
R 15 , R 16 , R 17 , R 18 independently represent a hydrogen atom, an SO 3 M group, a NO 2 group, a COOM group, a halogen atom, an ester group, an alkoxyl group having 1 to 6 carbon atoms, for a unsubstituted or substituted amide residue or sulfonamide residue each having up to 12 carbon atoms, said substituents being selected from the group consisting of COOM, OH, OCH 3 , NH 2 , Cl, COOCH 3 and COOCH 2 CH 3 .

Bevorzugt sind Trisazofarbstoffe der allgemeinen Formeln (IV) und (V), bei denen M, o und p die gleiche Bedeutung wie vorhin angegeben haben,

R1, R2, R3, R4, R5
unabhängig voneinander für ein Wasserstoffatom, eine SO3M-Gruppe, eine NO2-Gruppe eine COOM-Gruppe, eine CN-Gruppe, ein Halogenatom, einen Esterrest, einen Alkylrest oder Alkoxylrest mit je 1 bis 6 Kohlenstoffatomen stehen;
R6, R7, R8, R9, R10
unabhängig voneinander für ein Wasserstoffatom, eine SO3M-Gruppe eine NO2-Gruppe eine COOM-Gruppe, eine CN-Gruppe, ein Halogenatom, einen Esterrest, einen Alkylrest oder Alkoxylrest mit je 1 bis 6 Kohlenstoffatomen stehen;
R11, R12, R13, R14
unabhängig voneinander für ein Wasserstoffatom, ein Halogenatom, eine SO3M-Gruppe oder eine COOM-Gruppe stehen;
R15, R16, R17, R18
unabhängig voneinander für ein Wasserstoffatom, ein Halogenatom, eine SO3M-Gruppe oder eine COOM-Gruppe stehen
und
m, n
je den Wert 1 annehmen.
Preference is given to trisazo dyes of the general formulas (IV) and (V) in which M, O and P have the same meaning as stated above,
R 1 , R 2 , R 3 , R 4 , R 5
independently of one another represents a hydrogen atom, an SO 3 M group, an NO 2 group, a COOM group, a CN group, a halogen atom, an ester group, an alkyl group or alkoxyl group each having 1 to 6 carbon atoms;
R 6 , R 7 , R 8 , R 9 , R 10
independently of each other represents a hydrogen atom, an SO 3 M group, an NO 2 group, a COOM group, a CN group, a halogen atom, an ester group, an alkyl group or alkoxyl group each having 1 to 6 carbon atoms;
R 11 , R 12 , R 13 , R 14
independently represent a hydrogen atom, a halogen atom, an SO 3 M group or a COOM group;
R 15 , R 16 , R 17 , R 18
independently represent a hydrogen atom, a halogen atom, an SO 3 M group or a COOM group
and
m, n
each assume the value 1.

Besonders bevorzugt sind Trisazofarbstoffe der allgemeinen Formeln (IV) und (V), bei denen R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, M, o und p die gleiche Bedeutung wie vorhin angegeben haben und
die Sulfonsäuregruppen in den Positionen 4 und 4' stehen.Particular preference is given to trisazo dyes of the general formulas (IV) and (V) in which R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , M, o and p have the same meaning as previously stated and
the sulfonic acid groups are in positions 4 and 4 '.

Besonders bevorzugt sind Trisazofarbstoffe der allgemeinen Formeln (IV) und (V), in denen A ein Rest der allgemeinen Formel (VI) ist und B ein Rest der allgemeinen Formel (VIII).Particular preference is given to trisazo dyes of the general formulas (IV) and (V) in which A is a radical of the general formula (VI) and B is a radical of the general formula (VIII).

Ebenfalls bevorzugt sind Trisazofarbstoffe der allgemeinen Formeln (IV) und (V), in denen die Substituenten A und B identisch sind.Also preferred are trisazo dyes of the general formulas (IV) and (V) in which the substituents A and B are identical.

Bevorzugt werden als Metallkationen die Kationen der Alkalimetalle (Li, Na, K, Rb, Cs), der Erdalkalimetalle (Mg, Ca, Sr, Ba) und das Ammoniumkation, das gegebenenfalls einen oder mehrere Alkylreste mit je 1 bis 4 Kohlenstoffatomen oder mit einer Hydroxylgruppe substituierte Alkylreste mit jeweils 1 bis 6 Kohlenstoffatomen aufweist.Preferred metal cations are the cations of the alkali metals (Li, Na, K, Rb, Cs), the alkaline earth metals (Mg, Ca, Sr, Ba) and the ammonium cation which optionally has one or more alkyl radicals each having 1 to 4 carbon atoms or with one Hydroxyl group substituted alkyl having in each case 1 to 6 carbon atoms.

Spezifische Beispiele von Trisazofarbstoffen der allgemeinen Formel (IV) sind die folgenden, wobei der Substituent M in Tabelle 1 spezifiziert wird.

Figure imgb0010
Figure imgb0011
Figure imgb0012
Figure imgb0013
Figure imgb0014
Figure imgb0015
Figure imgb0016
Figure imgb0017
Figure imgb0018
Figure imgb0019
Figure imgb0020
Figure imgb0021
Figure imgb0022
Figure imgb0023
Figure imgb0024
Figure imgb0025
Figure imgb0026
 Specific examples of trisazo dyes of the general formula (IV) are as follows, wherein the substituent M is specified in Table 1.
Figure imgb0010
Figure imgb0011
Figure imgb0012
Figure imgb0013
Figure imgb0014
Figure imgb0015
Figure imgb0016
Figure imgb0017
Figure imgb0018
Figure imgb0019
Figure imgb0020
Figure imgb0021
Figure imgb0022
Figure imgb0023
Figure imgb0024
Figure imgb0025
Figure imgb0026

Spezifische Beispiele von Trisazofarbstoffen der allgemeinen Formel (IV) sind die folgenden, wobei der Substituent M in Tabelle 1 spezifiziert wird.

Figure imgb0027
Figure imgb0028
Figure imgb0029
Figure imgb0030
 Specific examples of trisazo dyes of the general formula (IV) are as follows, wherein the substituent M is specified in Table 1.
Figure imgb0027
Figure imgb0028
Figure imgb0029
Figure imgb0030

Die hergestellten Trisazofarbstoffe der allgemeinen Formel (IV) und (V) sind zusammen mit ihrem Absorptionsmaximum in wässriger Lösung in Tabelle 1 zusammengestellt: Tabelle 1 Farbstoff Nr. M λmax in H2O (nm) 10 Na 499 11 Na 501 12 Na 502 13 K 507 14 Li 505 15 Na 497 16 Na 509 17 Na 509 18 Na 508 19 Na 595 20 Na 507 21 Na 511 22 Na 500 23 Na 500 30 Na 509 31 Na 514 32 Na 501 33 K 498 The prepared trisazo dyes of the general formulas (IV) and (V) are listed together with their absorption maximum in aqueous solution in Table 1: Table 1 Dye no. M λ max in H 2 O (nm) 10 N / A 499 11 N / A 501 12 N / A 502 13 K 507 14 Li 505 15 N / A 497 16 N / A 509 17 N / A 509 18 N / A 508 19 N / A 595 20 N / A 507 21 N / A 511 22 N / A 500 23 N / A 500 30 N / A 509 31 N / A 514 32 N / A 501 33 K 498

Die Trisazofarbstoffe der allgemeinen Formeln (IV) und (V) können als freie Säuren oder als anorganische oder organische Salze dieser Säuren vorliegen. Vorzugsweise liegen sie in Form ihrer Alkali- oder Ammoniumsalze vor, wobei das Ammoniumkation substituiert sein kann. Beispiele solcher substituierter Ammoniumkationen sind 2-Hydroxyethylammonium, Bis-(2-hydroxyethyl)-ammonium, Tris-(2-hydroxyethyl)-ammonium, Bis-(2-hydroxyethyl)-methyl-ammonium, Tris-[2-(2-methoxyethoxy)-ethyl]-ammonium, 8-Hydroxy-3,6-dioxaoctylammonium und Tetraalkylammonium wie beispielsweise Tetramethylammonium oder Tetrabutylammonium.The trisazo dyes of the general formulas (IV) and (V) can be present as free acids or as inorganic or organic salts of these acids. Preferably, they are in the form of their alkali or ammonium salts, wherein the ammonium cation may be substituted. Examples of such substituted ammonium cations are 2-hydroxyethylammonium, bis (2-hydroxyethyl) ammonium, tris (2-hydroxyethyl) ammonium, bis (2-hydroxyethyl) methyl ammonium, tris [2- (2-methoxyethoxy ) -ethyl] -ammonium, 8-hydroxy-3,6-dioxaoctylammonium and tetraalkylammonium such as tetramethylammonium or tetrabutylammonium.

Weiter betrifft die Erfindung nicht nur reine Trisazofarbstoffe der allgemeinen Formeln (IV) und (V), sondern auch Gemische dieser Trisazofarbstoffe.Furthermore, the invention relates not only to pure trisazo dyes of the general formulas (IV) and (V), but also to mixtures of these trisazo dyes.

Die Erfindung betrifft weiterhin ein Verfahren zur Herstellung der erfindungsgemässen Trisazofarbstoffe der Formel (IV), das dadurch gekennzeichnet ist, dass
ein Amin der allgemeinen Formel (X)

Figure imgb0031
worin n und M die gleiche Bedeutung wie vorher angegeben haben, diazotiert und anschliessend mit einer Verbindung der allgemeinen Formel (XI),
Figure imgb0032
 worin m und M die gleiche Bedeutung wie vorher angegeben haben,
bei einem sauren pH-Wert zwischen etwa 1.0 und 3.0 gekuppelt wird, dass der intermediäre Farbstoff der allgemeinen Formel (XII) gebildet wird.
Figure imgb0033
 The invention furthermore relates to a process for the preparation of the trisazo dyes of the formula (IV) according to the invention, which is characterized in that
an amine of the general formula (X)
Figure imgb0031
 in which n and M have the same meaning as stated above, diazotized and then with a compound of general formula (XI),
Figure imgb0032
 where m and M have the same meaning as before,
is coupled at an acidic pH between about 1.0 and 3.0, that the intermediate dye of the general formula (XII) is formed.
Figure imgb0033

Der intermediäre Farbstoff der allgemeinen Formel (XII) wird weiter mit einer Diazoverbindung der allgemeinen Formel (XIII)

Figure imgb0034
worin R1, R2, R3, R4 und R5 die gleiche Bedeutung wie vorher angegeben haben und X das Anion der bei der Diazotierung verwendeten Säure ist,
oder der allgemeinen Formel (XIV)
Figure imgb0035
 worin R15, R16, R17, R18 und p die gleiche Bedeutung wie vorher angegeben haben und X das Anion der bei der Diazotierung verwendeten Säure ist,
bei einem leicht basischen pH-Wert zwischen etwa 7.0 und 9.0 gekuppelt und anschliessend basisch hydrolisiert wird,
so dass die intermediären Farbstoffe der allgemeinen Formel (XV)
Figure imgb0036
 oder der allgemeinen Formel (XVI)
Figure imgb0037
 gebildet werden.The intermediate dye of the general formula (XII) is further treated with a diazo compound of the general formula (XIII)
Figure imgb0034
 in which R 1 , R 2 , R 3 , R 4 and R 5 have the same meaning as stated above and X is the anion of the acid used in the diazotization,
or the general formula (XIV)
Figure imgb0035
 wherein R 15 , R 16 , R 17 , R 18 and p have the same meaning as before and X is the anion of the acid used in the diazotization,
coupled at a slightly basic pH between about 7.0 and 9.0 and then hydrolyzed basic,
such that the intermediate dyes of the general formula (XV)
Figure imgb0036
 or the general formula (XVI)
Figure imgb0037
 be formed.

Diese intermediären Farbstoff der allgemeinen Formeln (XV) und (XVI) werden weiter mit einer Diazoverbindung der allgemeinen Formel (XVII)

Figure imgb0038
worin X, R6, R7, R8, Rg und R10 die gleiche Bedeutung wie vorher angegeben haben,
oder der allgemeinen Formel (XVIII)
Figure imgb0039
 worin X, o, R11, R12, R13 und R14 die gleiche Bedeutung wie vorher angegeben haben,
bei einem etwa neutralen pH-Wert zwischen etwa 5.0 und 9.0 gekuppelt wird, so dass die erfindungsgemässen Farbstoffe der allgemeinen Formel (IV) gebildet werden.These intermediate dyes of the general formulas (XV) and (XVI) are further treated with a diazo compound of the general formula (XVII)
Figure imgb0038
 wherein X, R 6 , R 7 , R 8 , Rg and R 10 have the same meaning as before,
or the general formula (XVIII)
Figure imgb0039
 wherein X, O, R 11 , R 12 , R 13 and R 14 have the same meaning as stated above,
is coupled at an approximately neutral pH between about 5.0 and 9.0, so that the novel dyes of the general formula (IV) are formed.

Die Erfindung betrifft weiterhin ein Verfahren zur Herstellung der erfindungsgemässen Trisazofarbstoffe der allgemeinen Formel (V), das dadurch gekennzeichnet ist, dass
ein Amin der allgemeinen Formel (XIX)

Figure imgb0040
worin M, A und n die gleiche Bedeutung wie vorher angegeben haben, diazotiert und anschliessend mit einer Verbindung der allgemeinen Formel (XX)
Figure imgb0041
 worin M, B und m die gleiche Bedeutung wie vorher angegeben haben,
bei einem leicht basischen pH-Wert zwischen etwa 7.0 und 9.0 gekuppelt wird, so dass die erfindungsgemässen Trisazofarbstoffe der allgemeinen Formel (V) gebildet werden.The invention further relates to a process for preparing the novel trisazo dyes of the general formula (V), which is characterized in that
an amine of the general formula (XIX)
Figure imgb0040
 wherein M, A and n have the same meaning as stated above, diazotized and then with a compound of general formula (XX)
Figure imgb0041
 wherein M, B and m have the same meaning as before,
is coupled at a slightly basic pH between about 7.0 and 9.0, so that the novel trisazo dyes of the general formula (V) are formed.

Die erfindungsgemässen Trisazofarbstoffe der allgemeinen Formeln (IV) und (V) färben cellulosehaltige Materialien, Papier, Baumwolle und Viskose sowie Leder und Wolle mit guten Nass- und Lichtechtheiten.
Die Trisazofarbstoffe können nach allen in der Papier- und Textilindustrie für Substantivfarbstoffe gebräuchlichen Verfahren verwendet werden, insbesondere in der Massen- wie in der Oberflächenbehandlung von Papier für geleimte oder ungeleimte Sorten. Sie können auch in der Garn- und Stückfärberei von Baumwolle, Viskose und Leinen nach dem Ausziehverfahren oder im kontinuierlichen Verfahren angewandt werden.The trisazo dyes of the general formulas (IV) and (V) according to the invention dye cellulosic materials, paper, cotton and viscose, as well as leather and wool with good wet and light fastness properties.
The trisazo dyes can be used in accordance with all common practice in the paper and textile industry for substantive dyes, in particular in the bulk and surface treatment of paper for sized or unsized Sorts. They can also be used in the yarn and piece dyeing of cotton, viscose and linen by the exhaust process or in a continuous process.

Die erfindungsgemässen Trisazofarbstoffe sind besonders geeignet zum Aufzeichnen von Schrift und Bildern auf einem Aufzeichnungsmaterial, beschichtetem oder unbeschichtetem Papier, zum Färben und Bedrucken von natürlichen oder synthetischen Fasermaterialen, nanoporösen Aufzeichnungsmaterialien, Leder und Aluminium.The novel trisazo dyes are particularly suitable for recording writing and images on a recording material, coated or uncoated paper, for dyeing and printing natural or synthetic fiber materials, nanoporous recording materials, leather and aluminum.

Die Erfindung betrifft weiter flüssige Farbstoffpräparationen, die mindestens einen Trisazofarbstoff der allgemeinen Formeln (IV) oder (V) enthalten. Diese Anwendungsform ist insbesondere beim Färben von Papier bevorzugt. Die Herstellung von stabilen, flüssigen, vorzugsweise wässrigen, konzentrierten Färbepräparaten kann auf allgemein bekannte Weise erfolgen, vorteilhaft durch Lösen in geeigneten Lösungsmitteln. Von besonderem Vorteil ist die Herstellungsmöglichkeit solcher stabilen, wässrig-konzentrierten Präparationen im Zuge der Farbstoffsynthese selbst ohne Zwischenisolierung des Farbstoffs, beispielsweise nach einer Entsalzung der Reaktionslösung durch Diafiltration.The invention further relates to liquid dye preparations containing at least one trisazo dye of the general formulas (IV) or (V). This application form is particularly preferred in the dyeing of paper. The preparation of stable, liquid, preferably aqueous, concentrated dyeing preparations can be carried out in a generally known manner, advantageously by dissolving in suitable solvents. Of particular advantage is the possibility of preparing such stable, aqueous-concentrated preparations in the course of the dye synthesis itself without intermediate isolation of the dye, for example after desalting of the reaction solution by diafiltration.

Trisazofarbstoffe oder Mischungen von Trisazofarbstoffen der allgemeinen Formeln (IV) und (V) sind ausgezeichnete Farbstoffe zur Herstellung von Tinten für den Tintenstrahldruck und für Schreibutensilien.Trisazo dyes or mixtures of trisazo dyes of the general formulas (IV) and (V) are excellent dyes for the production of inks for ink-jet printing and writing utensils.

Die erfindungsgemässen schwarzen Trisazofarbstoffe der allgemeinen Formeln (IV) und (V) sind gut mit anderen Nuancierfarbstoffen, insbesondere solchen, wie sie beispielsweise in den Patentanmeldungen EP 0'755'984 , EP 1'219'682 , WO 96/24'635 und WO 96/24'636 beschrieben worden sind, kombinierbar, um einen noch neutraleren schwarzen Farbton zu erhalten.The inventive black trisazo dyes of the general formulas (IV) and (V) are good with other Nuancierfarbstoffen, in particular those, such as those in the patent applications EP 0'755'984 . EP 1'219'682 . WO 96/24635 and WO 96/24636 can be combined to obtain a more neutral black color.

Eine solche Tinte enthält eine oder mehrere der erfindungsgemässen Trisazofarbstoffe in einem flüssigen wässrigen Lösungsmittel. Die Tinte enthält 0.5 bis 20 Gewichtsprozent, vorzugsweise 0.5 bis 8 Gewichtsprozent dieser Trisazofarbstoffe, bezogen auf das Gesamtgewicht der Tinte. Das flüssige Lösungsmittel besteht vorzugsweise aus Wasser oder aus einer Mischung von Wasser und mit Wasser mischbaren organischen Lösungsmitteln. Geeignete Lösungsmittel sind beispielsweise im Patent US 4'626'284 und den Patentanmeldungen GB 2'289'473 , EP 0'176'195 , EP 0'415'581 , EP 0'425'150 und EP 0'597'672 beschrieben worden. Die vorliegende Erfindung wird durch die folgenden Beispiele näher beschrieben, ohne dass dadurch die beanspruchten Verbindungen in irgendeiner Weise eingeschränkt werden.Such an ink contains one or more of the trisazo dyes according to the invention in a liquid aqueous solvent. The ink contains 0.5 to 20 percent by weight, preferably 0.5 to 8 percent by weight of these trisazo dyes, based on the total weight of the ink. The liquid solvent is preferably water or a mixture of water and water-miscible organic solvents. Suitable solvents are, for example, in the patent US 4,626,284 and the patent applications GB 2'289'473 . EP 0'176'195 . EP 0'415'581 . EP 0'425'150 and EP 0'597'672 been described. The present invention will be further described by the following examples, without thereby limiting the claimed compounds in any way.

BeispieleExamples Beispiel 1example 1

Der Trisazofarbstoff Nr. 10 wurde folgendermassen hergestellt:Trisazo Dye No. 10 was prepared as follows:

Farbstoff-Diazokomponente:Dye-diazo component:

Die Verbindung der Formel (XXI)

Figure imgb0042
worin M für ein Wasserstoffatom steht, wurde aus 0.5 Mol 1-Amino-8-naphthol-4,6-disulfonsäure und 0.6 Mol Benzolsulfonylchlorid nach dem in der Patentanmeldung EP 1'693'422 im Beispiel 2-1 angegebenen Verfahren hergestellt.The compound of the formula (XXI)
Figure imgb0042
 wherein M is a hydrogen atom, was prepared from 0.5 mol of 1-amino-8-naphthol-4,6-disulfonic acid and 0.6 mol of benzenesulfonyl chloride according to the method specified in the patent application EP 1'693'422 in Example 2-1.

Diazosuspension ADiazo suspension A

46 g (0.1 Mol) der Verbindung der Formel (XXI) wurden bei Raumtemperatur in 360 ml Wasser suspendiert, auf eine Temperatur zwischen 0° C und 5° C abgekühlt und bei dieser Temperatur wurde unter Rühren während 10 Minuten 25 ml einer wässrigen Salzsäurelösung (37 %) zugetropft. Dann wurden bei einer Temperatur zwischen 0° C und 10° C 25 ml einer wässrigen Natriumnitritlösung (4N) zugetropft. Nach beendeter Zugabe wurde 1 Stunde bei einer Temperatur zwischen 0° C und 5° C nachgerührt. Die im Überschuss vorhandene salpetrige Säure wurde anschliessend durch Reaktion mit Sulfaminsäure entfernt.46 g (0.1 mol) of the compound of the formula (XXI) were suspended at room temperature in 360 ml of water, cooled to a temperature between 0 ° C. and 5 ° C., and 25 ml of an aqueous hydrochloric acid solution (10 ml) were stirred at this temperature for 10 minutes. 37%). Then, at a temperature between 0 ° C and 10 ° C, 25 ml of a sodium nitrite aqueous solution (4N) was added dropwise. After the addition was stirred for 1 hour at a temperature between 0 ° C and 5 ° C. The excess nitrous acid was then removed by reaction with sulfamic acid.

Herstellung des intermediären Farbstoffs der Formel (XXII)Preparation of the Intermediate Dye of Formula (XXII)

Bei einer Innentemperatur zwischen 5° C und 10° C wurde zur Suspension von 34.7 g (0.1 Mol) 1-Amino-8-naphthol-4,6-disulfonsäure (92 %) in 100 ml Wasser unter Rühren während 30 Minuten die Diazosuspension A zugegeben und der pH-Wert durch gleichzeitiges Zudosieren von Natronlauge (20 %) zwischen 2.0 und 3.0 gehalten. Nach beendeter Zugabe wurde 2 Stunden bei einer Temperatur zwischen 0° C und 5°C weitergerührt.

Figure imgb0043
At an internal temperature between 5 ° C and 10 ° C to the suspension of 34.7 g (0.1 mol) of 1-amino-8-naphthol-4,6-disulfonic acid (92%) in 100 ml of water with stirring for 30 minutes, the diazo suspension A added and the pH is maintained by simultaneous addition of sodium hydroxide solution (20%) between 2.0 and 3.0. After completion of the addition, stirring was continued for 2 hours at a temperature between 0 ° C and 5 ° C.
Figure imgb0043

Diazosuspension BDiazo suspension B

50.6 g (0.12 Mol) des Natriumsalzes der 2-Amino-5-nitrobenzolsulfonsäure (57 %) wurden in 350 ml Wasser aufgelöst. Die resultierende Lösung wurde auf eine Temperatur zwischen 0° C und 5° C abgekühlt und es wurden 30 ml einer wässrigen Lösung (4 N) von Natriumnitrit zugegeben. Bei einer Temperatur zwischen 0° C und 10°C wurde unter Rühren während 10 Minuten 50 ml einer wässrigen Salzsäurelösung (37 %) zugetropft. Dann wurde 1 Stunde bei dieser Temperatur weitergerührt. Die im Überschuss vorhandene salpetrige Säure wurde anschliessend durch Reaktion mit Sulfaminsäure entfernt.50.6 g (0.12 mol) of the sodium salt of 2-amino-5-nitrobenzenesulfonic acid (57%) were dissolved in 350 ml of water. The resulting solution was cooled to a temperature between 0 ° C and 5 ° C, and 30 ml of an aqueous solution (4N) of sodium nitrite was added. At a temperature between 0 ° C and 10 ° C with stirring for 10 minutes 50 ml of an aqueous hydrochloric acid solution (37%) was added dropwise. Then, stirring was continued for 1 hour at this temperature. The excess nitrous acid was then removed by reaction with sulfamic acid.

Herstellung des Farbstoffs der Formel (XXIII)Preparation of the dye of the formula (XXIII)

Der intermediäre Farbstoff der Formel (XXII) wurde nicht isoliert und direkt weiter mit der Diazoverbindung B umgesetzt.The intermediate dye of the formula (XXII) was not isolated and reacted further directly with the diazo compound B.

Bei einer Innentemperatur zwischen 5° C und 10° C wurde zur Suspension des intermediären Farbstoffs der Formel (XXIX) unter Rühren während 30 Minuten die Diazosuspension B zugegeben und der pH-Wert durch Zudosieren von Natronlauge (20 %) zwischen 5.0 und 7.0 gehalten. Nach beendeter Zugabe wurde 2 Stunden bei einer Temperatur zwischen 0° C und 5°C und 2 Stunden bei Raumtemperatur weitergerührt. Der intermediäre Farbstoff der Formel (XXVI) wurde nicht isoliert und direkt mit Natronlauge bei einer Temperatur von 90° C und einem pH-Wert zwischen 11.0 und 12.0 hydrolysiert. Nach beendeter Hydrolyse wurde der pH-Wert mit Essigsäure auf 7.0 abgesenkt und der ausgefallene Farbstoff abgenutscht. Der Rohfarbstoff wurde mit 300 ml einer wässrigen Lösung (60 %) von Ethanol gereinigt. Nach Trocknung des Farbstoffs erhielt man 39.2 g des Farbstoffs der Formel (XXIII).

Figure imgb0044
At an internal temperature of between 5 ° C. and 10 ° C., the diazo suspension B was added to the suspension of the intermediate dye of the formula (XXIX) with stirring for 30 minutes and the pH was maintained at between 5.0 and 7.0 by metering in sodium hydroxide (20%). After completion of the addition, the mixture was further stirred for 2 hours at a temperature between 0 ° C and 5 ° C and 2 hours at room temperature. The intermediate dye of formula (XXVI) was not isolated and hydrolyzed directly with caustic soda at a temperature of 90 ° C and a pH between 11.0 and 12.0. After completion of the hydrolysis, the pH was lowered to 7.0 with acetic acid and the precipitated dye was filtered off with suction. The crude dye was cleaned with 300 ml of an aqueous solution (60%) of ethanol. After the dye had dried, 39.2 g of the dye of the formula (XXIII) were obtained.
Figure imgb0044

Herstellung des Trisazofarbstoffs (10)Preparation of Trisazo Dye (10)

Zu einem homogenen Gemisch von 9.9 g (10 mMol) des Farbstoffs der Formel (XXIII) in 150 ml einer Mischung von Wasser und N-Methylpyrrolidon (2 : 1) bei einer Innentemperatur zwischen 0° C und 5° C wurden während 30 Minuten 15 mMol der Diazosuspension B zugegeben und der pH-Wert durch gleichzeitiges Zudosieren von Natronlauge (20 %) zwischen 5.0 und 7.0 gehalten. Nach beendeter Zugabe wurde 2 Stunden bei einer Temperatur zwischen 0° C und 5° C und 2 Stunden bei Raumtemperatur weitergerührt. Dann wurde die dunkle Lösung klarfiltriert und das Filtrat am Rotavapor aufkonzentriert. Der Farbstoff wurde dann durch Zugabe von Methanol ausgefällt und abfiltriert.. Der Rohfarbstoff wurde mit 60 ml einer wässrigen Lösung (80 %) von Ethanol gereinigt. Nach Trocknung erhielt man 10 g des Triazofarbstoffs 10 in Form seines Natriumsalzes.To a homogeneous mixture of 9.9 g (10 mmol) of the dye of formula (XXIII) in 150 ml of a mixture of water and N-methylpyrrolidone (2: 1) at an internal temperature of between 0 ° C and 5 ° C was added 15 minutes mmol of diazo suspension B was added and the pH was maintained by simultaneous addition of sodium hydroxide solution (20%) between 5.0 and 7.0. After completion of the addition, the mixture was further stirred for 2 hours at a temperature between 0 ° C and 5 ° C and 2 hours at room temperature. Then the dark solution was clarified by filtration and the filtrate concentrated on a Rotavapor. The dye was then precipitated by addition of methanol and filtered off. The crude dye was purified with 60 ml of an aqueous solution (80%) of ethanol. After drying, 10 g of the triazo dye 10 were obtained in the form of its sodium salt.

Auf ähnliche Art und Weise können durch die Wahl geeigneter Ausgangsmaterialien die erfindungsgemässen Trisazofarbstoffe 11 bis 26 hergestellt werden.In a similar manner, by selecting suitable starting materials, the trisazo dyes 11 to 26 according to the invention can be prepared.

Die Trisazofarbstoffe (31) bis (34) können nach dem Verfahren hergestellt werden, das in der Patentanmeldung EP 10187827.0 beschrieben worden ist.The trisazo dyes (31) to (34) can be prepared by the method described in the patent application EP 10187827.0 has been described.

Herstellungsbeispiel für TintenProduction example of inks

Die vorliegende Erfindung wird, soweit sie sich auf Tinten bezieht, durch die folgenden Beispiele beschrieben, in denen erfindungsgemässe Trisazofarbstoffe aus der Tabelle 1 und Trisazofarbstoffe des Standes der Technik eingesetzt werden. 100 g jeder Tinte wurden hergestellt, indem die benötigte Menge Farbstoff (2 - 9 g), Glycerin (5 g), Ethylenglykol (5 g), Tergitol 15-S-7 (erhältlich bei Union Carbide Co., Houston, USA) (0.5 g) und eine Biocid-Lösung (Mergal K 10N, erhältlich bei Riedel-de-Haën, Seelze, Deutschland) (0.2 g) zusammen mit Wasser etwa 1 Stunde unter Rühren auf eine Temperatur von 50° C erwärmt wurden. Die erhaltene Lösung wurde auf eine Temperatur von 20° C abgekühlt und ihr pH-Wert auf 7.5 eingestellt. Anschliessend wurde die Lösung durch ein Millipore®-Filter mit 0.5 µm Porendurchmesser abfiltriert. Die Farbstoffmenge wurde so gewählt, dass die optische Dichte des bedruckten Bildes für alle Farbstoffe möglichst gleich war.The present invention, as far as it relates to inks, is described by the following examples in which trisazo dyes according to the invention from Table 1 and trisazo dyes of the prior art are used. 100 g of each ink was prepared by adding the required amount of dye (2-9 g), glycerol (5 g), ethylene glycol (5 g), Tergitol 15-S-7 (available from Union Carbide Co., Houston, USA) ( 0.5 g) and a biocide solution (Mergal K 10N, available from Riedel-de-Haën, Seelze, Germany) (0.2 g) were heated together with water for about 1 hour with stirring to a temperature of 50 ° C. The resulting solution was cooled to a temperature of 20 ° C and adjusted its pH to 7.5. Subsequently, the solution was filtered through a Millipore ® filter with 0.5 micron pore diameter. The amount of dye was chosen so that the optical density of the printed image for all dyes was as equal as possible.

Anwendungsbeispiele von TintenApplication examples of inks

Die hergestellten Tinten wurden anschliessend mit Hilfe eines Tintenstrahldruckers des Typs Pixma iP4000 von Canon auf die folgenden Aufnahmematerialen aufgebracht

  1. 1) ILFORD Premium Plus Instant Dry Glossy Photo RC Paper (nanoporöses Aufzeichnungsmaterial auf Basis von Siliziumdioxid, erhältlich bei ILFORD Imaging Switzerland GmbH, Freiburg, Schweiz)
    und
  2. 2) ILFORD Galerie Smooth Gloss Paper (nanoporöses Aufzeichnungsmaterial auf Basis von Aluminiumoxid/hydroxid, erhältlich bei ILFORD Imaging Switzerland GmbH, Freiburg, Schweiz)
The prepared inks were then applied to the following recording materials using a Canon Pixma iP4000 inkjet printer
  1. 1) ILFORD Premium Plus Instant Dry Glossy Photo RC Paper (nanoporous recording material based on silicon dioxide, available from ILFORD Imaging Switzerland GmbH, Freiburg, Switzerland)
    and
  2. 2) ILFORD Gallery Smooth Gloss Paper (nanoporous recording material based on alumina / hydroxide, available from ILFORD Imaging Switzerland GmbH, Freiburg, Switzerland)

Prüfungenexams (A) Lichtechtheit (A) lightfastness

Die bedruckten Muster werden in einem Weather-Ometer® Ci35A (erhältlich bei Atlas Material Testing Technology, Chicago, USA) mit einer 6500 W Xenon Lampe bei einer Temperatur von 20° C and einer relativen Luftfeuchtigkeit von 50 % so lange bestrahlt, bis 20 Megaluxstunden erreicht wurden. Der Dichteverlust wurde mit einem Spektrophotometer Spectrolino® gemessen. Der prozentuale Dichteverlust ausgehend von der ursprünglichen Dichte ist ein Mass für die Lichtechtheit der Farbstoffe auf dem bedruckten Aufzeichnungsmaterial.The printed samples are irradiated in a Weather-Ometer® Ci35A (available from Atlas Material Testing Technology, Chicago, USA) with a 6500 W xenon lamp at a temperature of 20 ° C and a relative humidity of 50% until 20 megalux hours were achieved. The density loss was measured with a spectrophotometer Spectrolino ®. The percent density loss from the original density is a measure of the light fastness of the dyes on the printed recording material.

(B) Farbkoordinaten (B) Color coordinates

Die L*a*b*-Werte wurden auf bedruckten Mustern mit Hilfe eines Spektrometers Gretag SPM 100, erhältlich bei Gretag AG, Regensdorf, Schweiz, gemessen.The L * a * b * values were measured on printed samples using a spectrometer Gretag SPM 100, available from Gretag AG, Regensdorf, Switzerland.

(C) Ozonbeständigkeit (C) ozone resistance

Quadratische Farbfelder mit einer Fläche von 1 cm2 wurden auf die beiden Aufzeichnungsmaterialien gedruckt. Die bedruckten Muster werden 24 Stunden bei einer relativen Luftfeuchtigkeit von etwa 60 % getrocknet. Darauf werden an den bedruckten Mustern die optische Dichte der quadratischen Farbfelder mit einem Densitometer Spectrolino® der Firma Gretag Macbeth, Regensdorf, Schweiz gemessen. Anschliessend werden die bedruckten Muster in einer Ozonkammer, Modell 903, der Firma Satra/Hampden, Grossbritannien, bei einer Temperatur von 30° C, einer relativen Luftfeuchtigkeit von 50 % und einer Ozonkonzentration von 1 ppm bei einer Geschwindigkeit der zirkulierenden, ozonhaltigen Luft von 13 mm/s während einer bestimmten Zeit gelagert. Nach abgeschlossener Lagerung werden die Muster erneut ausgemessen. Die Dichteunterschiede in Prozenten vor und nach der Lagerung sind ein Mass für das Ausmass des Farbstoffverlustes durch die Einwirkung des Ozons.Square color patches with an area of 1 cm 2 were printed on the two recording materials. The printed samples are dried for 24 hours at a relative humidity of about 60%. Thereafter, the optical density of the colored squares with a densitometer Spectrolino ® from Gretag Macbeth, Regensdorf, Switzerland be measured on the printed samples. The printed samples are then placed in an ozone chamber, Model 903, Satra / Hampden, UK, at a temperature of 30 ° C, a relative humidity of 50% and an ozone concentration of 1 ppm at a circulating ozone air velocity of 13 mm / s stored for a certain time. After completion of storage, the samples are measured again. Density differences in percentages before and after storage are a measure of the extent of dye loss due to the action of ozone.

ErgebnisseResults

Die Dichteverluste bei einer Bestrahlung mit 20 Megaluxstunden sind in Tabelle 2 zusammengestellt. Tabelle 2 Farbstoff Nr. Prozentualer Dichteverlust Aufzeichnungsmaterial 1 Prozentualer Dichteverlust Aufzeichnungsmaterial 2 10 8.7 18.8 11 7.2 24.3 12 13.1 25.0 13 7.2 24.3 14 13.0 32.8 15 15.9 35.6 16 7.9 26.8 17 16.3 39.2 18 15.1 29.7 19 17.8 39.4 20 13.3 31.9 21 17.0 35.6 31 15.7 30.5 (I) 19.7 34.0 (II) 39.4 62.0 The density losses during irradiation with 20 megalux hours are summarized in Table 2. Table 2 Dye no. Percentage density loss of recording material 1 Percentage density loss recording material 2 10 8.7 18.8 11 7.2 24.3 12 13.1 25.0 13 7.2 24.3 14 13.0 32.8 15 15.9 35.6 16 7.9 26.8 17 16.3 39.2 18 15.1 29.7 19 17.8 39.4 20 13.3 31.9 21 17.0 35.6 31 15.7 30.5 (I) 19.7 34.0 (II) 39.4 62.0

Ein Vergleich der gemessenen Farbstoffverluste von bedruckten Mustern in Tabelle 2 zeigt klar, dass die erfindungsgemässen Trisazoschwarzfarbstoffe im Vergleich zu den Trisazoschwarzfarbstoffen (I) und (II) des Standes der Technik eine wesentlich besser Lichtbeständigkeiten zeigen. Das heisst, dass im Tintenstrahldruck hergestellte schwarze Abbildungen mit den erfindungsgemässen Trisazoschwarzfarbstoffen auch unter Lichteinfluss viel weniger verblassen als schwarze Bilder, welche die bisher bekannten Trisazoschwarzfarbstoffe des Standes der Technik enthalten.A comparison of the measured dye losses of printed patterns in Table 2 clearly shows that the trisazo black dyes according to the invention exhibit a significantly better light resistance compared to the trisazo black dyes (I) and (II) of the prior art. That is, black images prepared by ink-jet printing with the trisazo black dyes of the invention fade much less even under the influence of light than black images containing the hitherto known trisazo black dyes of the prior art.

Die L*a*b*-Werte (Lichtart D65) sind in Tabelle 3 für die erfindungsgemässen und für die Trisazoschwarzfarbstoffe (I) und (II) des Standes der Technik zusammengestellt. Tabelle 3 Farbstoff Nr. L*a*b*-Wert Aufzeichnungsmaterial 1 L*a*b*-Wert Aufzeichnungsmaterial 2 10 15.4 / 4.5 / -1.9 11.9 / 4.9 / -2.3 11 7.8 / 5.7 / -7.4 7.2 / 4.5 / -8.0 12 10.8 / 6.4 / -9.6 9.8 / 11.9 / -3.0 13 7.8 / 5.7 / -7.4 7.2 / 4.5 / -8.0 14 6.3 / 1.6 / -5.8 6.3 / 1.7 / -6.2 15 8.9 / 2.4 / -5.6 7.8 / 2.8 / -6.9 16 8.1 / 3.4 / -5.8 8.6 / 3.4 / -7.1 17 17.0 / 10.8 / -6.5 8.2 / 7.4 / -7.7 18 10.2 / 4.7 / -6.6 8.3 / 4.6 / -8.1 19 7.5 / 3.6 / -8.3 7.3 / 2.3 / -7.3 20 9.3 / 6.3 / -7.7 8.0 / 5.5 / -8.1 21 12.0 / 6.5 / -6.5 10.6 / 5.6 / -7.3 31 10.4 / 6.4 / -5.7 9.6 / 5.4 / -6.0 33 13.7 / 5.1 / -4.8 (I) 9.1 / 9.2 / -21.5 8.6 / 7.8 / -18.1 (II) 18.9 / 4.3 / -31.7 21.0 / 11.4 / -27.0 The L * a * b * values (type of light D 65 ) are listed in Table 3 for the novel and for the trisazo black dyes (I) and (II) of the prior art. Table 3 Dye no. L * a * b * value Recording material 1 L * a * b * value recording material 2 10 15.4 / 4.5 / -1.9 11.9 / 4.9 / -2.3 11 7.8 / 5.7 / -7.4 7.2 / 4.5 / -8.0 12 10.8 / 6.4 / -9.6 9.8 / 11.9 / -3.0 13 7.8 / 5.7 / -7.4 7.2 / 4.5 / -8.0 14 6.3 / 1.6 / -5.8 6.3 / 1.7 / -6.2 15 8.9 / 2.4 / -5.6 7.8 / 2.8 / -6.9 16 8.1 / 3.4 / -5.8 8.6 / 3.4 / -7.1 17 17.0 / 10.8 / -6.5 8.2 / 7.4 / -7.7 18 10.2 / 4.7 / -6.6 8.3 / 4.6 / -8.1 19 7.5 / 3.6 / -8.3 7.3 / 2.3 / -7.3 20 9.3 / 6.3 / -7.7 8.0 / 5.5 / -8.1 21 12.0 / 6.5 / -6.5 10.6 / 5.6 / -7.3 31 10.4 / 6.4 / -5.7 9.6 / 5.4 / -6.0 33 13.7 / 5.1 / -4.8 (I) 9.1 / 9.2 / -21.5 8.6 / 7.8 / -18.1 (II) 18.9 / 4.3 / -31.7 21.0 / 11.4 / -27.0

Ein Vergleich der gemessenen L*a*b*-Werte in Tabelle 3, in denen die Tinten die erfindungsgemässen Trisazofarbstoffe aus Tabelle 1 enthalten, zeigt klar, dass Bildstellen mit den Tinten, welche die erfindungsgemässen Trisazofarbstoffen enthalten, kleinere b*-Werte aufweisen als Bildstellen mit den Tinten, welche die Trisazofarbstoffe (I) und (II) des Standes der Technik enthalten. Die erfindungsgemässen schwarzen Trisazofarbstoffe sind deshalb im Tintenstrahldruckverfahren besonderst geeignet, weil sie eine neutralere Schwarzwiedergaben ermöglichen.A comparison of the measured L * a * b * values in Table 3, in which the inks contain the novel trisazo dyes from Table 1, clearly shows that image sites with the inks containing the trisazo dyes according to the invention have lower b * values than Image locations with the inks containing the trisazo dyes (I) and (II) of the prior art. The novel black trisazo dyes are therefore particularly suitable in the ink-jet printing process, because they allow a more neutral black rendition.

Die bestimmten Werte für die Farbstoffverluste bei einem Tintenauftrag von 80 % durch die Ozoneinwirkung auf den Aufzeichnungsmaterialen 1) und 2) nach 96 Stunden Exposition an ozonhaltiger Luft sind in Tabelle 4 aufgeführt. Tabelle 4 Farbstoff Nr. Prozentualer Dichteverlust Aufzeichnungsmaterial 1 Prozentualer Dichteverlust Aufzeichnungsmaterial 2 10 13.9 23.8 11 11.4 17.3 12 32.0 48.3 13 13.8 25.0 14 15.0 28.2 15 18.3 31.5 16 13.6 22.7 17 20.7 34.5 18 18.0 31.3 19 18.7 26.4 20 13.3 31.9 21 35.2 43.8 31 28.4 34.0 (I) 14.2 17.1 (II) 48.5 48.2 The determined values for the dye losses at 80% ink application by the ozone action on the recording materials 1) and 2) after 96 hours exposure to ozone-containing air are shown in Table 4. Table 4 Dye no. Percentage density loss of recording material 1 Percentage density loss recording material 2 10 13.9 23.8 11 11.4 17.3 12 32.0 48.3 13 13.8 25.0 14 15.0 28.2 15 18.3 31.5 16 13.6 22.7 17 20.7 34.5 18 18.0 31.3 19 18.7 26.4 20 13.3 31.9 21 35.2 43.8 31 28.4 34.0 (I) 14.2 17.1 (II) 48.5 48.2

Ein Vergleich der gemessenen Ozonbeständigkeiten in Tabelle 4, in denen die Tinten die erfindungsgemässen Trisazofarbstoffe aus Tabelle 2 enthalten, zeigt klar, dass die erfindungsgemässen Trisazofarbstoffe eine bessere Ozonbeständigkeit haben als der Trisazofarbstoff (II) des Standes der Technik.A comparison of the measured ozone resistances in Table 4, in which the inks contain the novel trisazo dyes from Table 2, clearly shows that the trisazo dyes according to the invention have a better ozone resistance than the trisazo dye (II) of the prior art.

Claims (12)

  1. Trisazo dyes of the general formula (IV)
    Figure imgb0062
     and of the general formula (V)
    Figure imgb0063
     wherein
    M represents a hydrogen atom, a metal cation or an ammonium cation, which optionally has one or more unsubstituted or substituted alkyl radicals or hydroxyalkoxyalkyl radicals having in each case 1 to 18 carbon atoms;
    m, n independently of each other assume the value 0 or 1;
    A either represents a radical of the general formula (VI)
    Figure imgb0064
     wherein
    R6, R7, R8, R9, R10 independently of each other represent a hydrogen atom, an SO3M group, an NO2 group, a COOM group, a CN group, a halogen atom, an ester radical, an alkyl radical or alkoxy radical each having 1 to 6 carbon atoms, an unsubstituted or substituted amide radical or sulphonamide radical each having up to 12 carbon atoms, the substituents being chosen from the group consisting of COOM, OH, OCH3, NH2, Cl, COOCH3 and COOCH2CH3;
    or represents a radical of the general formula (VII)
    Figure imgb0065
     wherein
    o assumes the value 0 or 1
    and R11, R12, R13, R14 independently of each other represent a hydrogen atom, an SO3M group, an NO2 group, a COOM group, a halogen atom, an ester radical, an alkoxy radical having 1 to 6 carbon atoms, an unsubstituted or substituted amide radical or sulphonamide radical each having up to 12 carbon atoms, the substituents being chosen from the group consisting of COOM, OH, OCH3, NH2, Cl, COOCH3 and COOCH2CH3, and
    B either represents a radical of the general formula (VIII)
    Figure imgb0066
     wherein
    R1, R2, R3, R4, R5 independently of each other represent a hydrogen atom, an SO3M group, an NO2 group, a COOM group, a CN group, a halogen atom, an ester radical, an alkyl radical or alkoxy radical each having 1 to 6 carbon atoms, an unsubstituted or substituted amide radical or sulphonamide radical each having up to 12 carbon atoms, the substituents being chosen from the group consisting of COOM, OH, OCH3, NH2, Cl, COOCH3 and COOCH2CH3;
    or represents a radical of the general formula (IX)
    Figure imgb0067
     wherein
    p assumes the value 0 or 1
    and R15, R16, R17, R18 independently of each other represent a hydrogen atom, an SO3M group, an NO2 group, a COOM group, a halogen atom, an ester radical, an alkoxy radical having 1 to 6 carbon atoms, an unsubstituted or substituted amide radical or sulphonamide radical each having up to 12 carbon atoms, the substituents being chosen from the group consisting of COOM, OH, OCH3, NH2, Cl, COOCH3 and COOCH2CH3.
  2. Trisazo dyes of the general formulae (IV) and (V) according to claim 1, characterized in that
    M, o and p have the same meaning as in claim 1,
    R1, R2, R3, R4, R5 independently of each other represent a hydrogen atom, an SO3M group, an NO2 group, a COOM group, a CN group, a halogen atom, an ester radical, an alkyl radical or alkoxy radical each having 1 to 6 carbon atoms;
    R6, R7, R8, R9, R10 independently of each other represent a hydrogen atom, an SO3M group, an NO2 group, a COOM group, a CN group, a halogen atom, an ester radical, an alkyl radical or alkoxy radical each having 1 to 6 carbon atoms;
    R11, R12, R13, R14 independently of each other represent a hydrogen atom, a halogen atom, an SO3M group or a COOM group;
    R15, R16, R17, R18 independently of each other represent a hydrogen atom, a halogen atom, an SO3M group or a COOM group;
    and
    m, n each assume the value 1.
  3. Trisazo dyes of the general formulae (IV) and (V) according to claim 1, characterized in that
    R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, M, o and p have the same meaning as in claim 1;
    m, n each assume the value 1
    and
    the sulphonic acid groups are in positions 4 and 4'.
  4. Trisazo dyes of the general formulae (IV) and (V) according to claim 1, characterized in that
    M, o and p have the same meaning as in claim 1;
    R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17 and R18 have the same meaning as in claim 2;
    m, n each assume the value 1
    and
    the sulphonic acid groups are in positions 4 and 4'.
  5. Trisazo dyes of the general formulae (IV) and (V) according to claims 1 to 4,
    characterized in that
    A is a radical of the general formula (VII) and B is a radical of the general formula (IX).
  6. Trisazo dyes of the general formulae (IV) and (V) according to claims 1 to 5,
    characterized in that
    the substituents A and B are identical.
  7. Process for the preparation of the trisazo dyes of the general formula (IV) according to the invention according to claim 1, characterized in that
    an amine of the general formula (X)
    Figure imgb0068
     wherein n and M have the same meaning as in claim 1,
    is diazotized and the diazotization product is then coupled with a compound of the general formula (XI)
    Figure imgb0069
     wherein m and M have the same meaning as in claim 1,
    at an acid pH of between about 1.0 and 3.0, in that the intermediate dye of the general formula (XII) is formed
    Figure imgb0070
     the intermediate dye of the general formula (XII) is coupled further with a diazo compound of the general formula (XIII)
    Figure imgb0071
     wherein R1, R2, R3, R4 and R5 have the same meaning as in claim 1 and X is the anion of the acid used in the diazotization,
    or of the general formula (XIV)
    Figure imgb0072
     wherein R15, R16, R17, R18 and p have the same meaning as in claim 1 and X is the anion of the acid used in the diazotization,
    at a slightly basic pH of between about 7.0 and 9.0 and the coupling product is then subjected to hydrolysis under basic conditions, to form the intermediate dyes of the general formula (XV)
    Figure imgb0073
     or of the general formula (XVI)
    Figure imgb0074
     which are then coupled further with a diazo compound of the general formula (XVII)
    Figure imgb0075
     wherein R6, R7, R8, R9 and R10 have the same meaning as in claim 1 and X is the anion of the acid used in the diazotization,
    or of the general formula (XVIII)
    Figure imgb0076
     wherein o, R11, R12, R13 and R14 have the same meaning as given above and X is the anion of the acid used in the diazotization,
    at an approximately neutral pH of between about 5.0 and 9.0.
  8. Process for the preparation of the trisazo dyestuffs of the general formula (V) according to the invention according to claim 1, characterized in that
    an amine of the general formula (XIX)
    Figure imgb0077
     wherein M, A and n have the same meaning as in claim 1,
    is diazotized and the diazotization product is then coupled with a compound of the general formula (XX)
    Figure imgb0078
     wherein M, B and m have the same meaning as in claim 1,
    at a slightly basic pH of between about 7.0 and 9.0.
  9. Use of the trisazo dyes according to one or more of claims 1 to 6 for recording script and images on a recording material, coated or non-coated paper, for dyeing and printing natural or synthetic fibre materials, nanoporous recording materials, leather and aluminium.
  10. Liquid dye preparations which comprise at least one trisazo dye or a mixture of trisazo dyes according to one or more of claims 1 to 6.
  11. Inks for inkjet printing and for writing implements, which comprise at least one trisazo dye or a mixture of trisazo dyes according to one or more of claims 1 to 6.
  12. Inks for inkjet printing and for writing implements, which comprise, in addition to at least one trisazo dye or a mixture of trisazo dyes according to one or more of claims 1 to 6, one or more further dyes.
EP10196679.4A 2010-12-22 2010-12-22 Black trisazo dyes, their preparation and their use Active EP2468822B1 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
EP10196679.4A EP2468822B1 (en) 2010-12-22 2010-12-22 Black trisazo dyes, their preparation and their use
AU2011253851A AU2011253851B2 (en) 2010-12-22 2011-12-06 Black trisazo dyes, their preparation and their use
JP2011280567A JP5712406B2 (en) 2010-12-22 2011-12-21 Black trisazo dye, method for preparing and using the trisazo dye
CN201110432311.1A CN102558899B (en) 2010-12-22 2011-12-21 Black trisazo dyestuff, production and use thereof
KR1020110138862A KR20120089999A (en) 2010-12-22 2011-12-21 Black trisazo dyes, their preparation and their use
US13/335,219 US8361168B2 (en) 2010-12-22 2011-12-22 Black trisazo dyes, their preparation and their use

Applications Claiming Priority (1)

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EP10196679.4A EP2468822B1 (en) 2010-12-22 2010-12-22 Black trisazo dyes, their preparation and their use

Related Child Applications (1)

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EP14001577 Division-Into 2014-05-06

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EP2468822A1 EP2468822A1 (en) 2012-06-27
EP2468822B1 true EP2468822B1 (en) 2015-06-10

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US (1) US8361168B2 (en)
EP (1) EP2468822B1 (en)
JP (1) JP5712406B2 (en)
KR (1) KR20120089999A (en)
CN (1) CN102558899B (en)
AU (1) AU2011253851B2 (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2641940A1 (en) * 2012-03-22 2013-09-25 ILFORD Imaging Switzerland GmbH Water soluble and water fast dyes for ink jet printing
MX2014015540A (en) * 2012-06-18 2015-06-23 Dystar Colours Distrib Gmbh Metal-free reactive dyes, process for the production thereof and their use.
CN103554994B (en) * 2013-09-27 2016-03-16 沈钢 A kind of high colour-fast rate aterrimus polyazo reactive dyestuffs and application
TWI667293B (en) * 2015-03-16 2019-08-01 瑞士商亞齊羅馬Ｉｐ公司 Trisazo acid dyes, a process for preparing the same, use thereof, a process for dyeing or printing a substrate and a colour-containing substrate by using the same, and dye composition having the same

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GB8421551D0 (en) 1984-08-24 1984-09-26 Ici Plc Water-soluble dye
US4963189A (en) 1989-08-24 1990-10-16 Hewlett-Packard Company Waterfast ink formulations with a novel series of anionic dyes containing two or more carboxyl groups
US5062892A (en) 1989-10-27 1991-11-05 Hewlett-Packard Company Ink additives for improved ink-jet performance
US5439517A (en) 1992-11-09 1995-08-08 Seiko Epson Corporation Black ink composition excellent in black
GB9409921D0 (en) 1994-05-18 1994-07-06 Zeneca Ltd Compounds
GB9502334D0 (en) 1995-02-07 1995-03-29 Ilford Ag Yellow dyes
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Also Published As

Publication number Publication date
EP2468822A1 (en) 2012-06-27
CN102558899B (en) 2015-05-27
US8361168B2 (en) 2013-01-29
CN102558899A (en) 2012-07-11
JP5712406B2 (en) 2015-05-07
AU2011253851B2 (en) 2013-01-10
KR20120089999A (en) 2012-08-16
JP2012132009A (en) 2012-07-12
US20120159719A1 (en) 2012-06-28
AU2011253851A1 (en) 2012-07-12

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